Desulfurization of heavy liquid hydrocarbon with carbon monoxide at high pressure

ABSTRACT

A HEAVY HYDROCARBON FEEDSTOCK IS UPGRADED BY AT LEAST ONE OF THE PROCESS OF DESULFURIZATION, DECREASING CARBON RESIDUES, INCREASING API GRAVITY, AND LIQUEFACTION OF SOLID FEEDSTOCK BY REACTING THE FEEDSTOCK AT ELEVATED TEMPERATURE AND PRESSURE IN THE PRESENCE OF CARBON MONOXIDE AND IN THE PRESENCE OF A CATALYTICALLY ACTIVE METAL. IN ONE EMBODIMENT THE ACTIVE METLLIC CATALYST IS ASSOCIATED WITH MINOR AMOUNTS OF ALKALI OR ALKALINE EARTH METALS TO MINIMIZE PROMOTION OF CRACKING SIDE REACTIONS. IN A PREFERRED EMBODIMENT A HEAVY HYDROCARBON FEEDSTOCK IS UPGRADED IN THE PRESENCE OF THE CATALYST SYSTEM FORMED FROM A BARIUM SALT WHICH HAS BEEN DEPOSITED ON COBALT MOLYBDATE DISPERSED ON AN ALUMINA SUPPORT.

United States Patent Office 3,728,252 Patented Apr. 17, 19,73

ABSTRACT OF THE DISCLOSURE A heavy hydrocarbon feedstock is upgraded byat least one of the processes of desulfurization, decreasing car-bonresidues, increasing API gravity, and liquefaction of solid feedstock byreacting the feedstock at elevated temperature and pressure in thepresence of carbon monoxide and in the presence of a catalyticallyactive metal. In one embodiment the active metallic catalyst isassociated with minor amounts of alkali or alkaline earth metals tominimize promotion of cracking side reactions. In a pre ferredembodiment a heavy hydrocarbon feedstock is upgraded in the presence ofthe catalyst system formed from a barium salt which has been depositedon cobalt molybdate dispersed on an alumina support.

CROSS-REFERENCES TO RELATED APPLICATIONS In my co-pending applicationSer. No. 757,113, filed Oct. 3, 1968, now Pat. No. 3,586,621 isdisclosed amethod for desulfurizing heavy hydrocarbon feeds bycontacting such feeds with steam in the presence of suitable catalysts.The effectiveness of that process is believed to be due to theoccurrence of reactions such as the water-gas shift reaction and thehydrogenation reaction.

It has now been found that still more improved results can be obtainedby contacting heavy hydrocarbon-containing feeds with carbon monoxide ineither the presence or absence of steam over suitable catalysts. Notonly are beneficial results obtained at temperatures which are generallylower than those of the above-described filed case, but also benefitsother than desulfurization are obtained.

BACKGROUND OF INVENTION This invention relates to the upgrading of heavyhydrocarbon feedstocks. In one of its aspects, this invention relates tomultiple purpose catalysts. In another of its aspects, this inventionrelates to effecting multiple reactions with a single catalyst system.In still another of its aspects, this invention relates todesulfurization of hydrocarbon feedstocks. In still another of itsaspects, this invention relates to decreasing carbon residues inhydrocarbon feedstocks. In yet another of its aspects, this inventionrelates to liquefaction of solid hydrocarbons in feedstock materials. Inyet another of its aspects, this invention relates to increasing the APIgravity of hydro carbon feedstocks.

In one of its concepts, this invention provides a method for performingat least one reaction chosen from: desulfurizing a hydrocarbonfeedstock, decreasing the carbon residues in a hydrocarbon feedstock,increasing the API gravity of a hydrocarbon feedstock, or liquefying asolid hydrocarbon in hydrocarbon feedstock material using an activemetal catalyst. Another of its concepts, this invention provides amethod for simultaneously catalyzing multiple chemical reactions usingactive metal catalysts.

Catalytic methods that can desulfurize, increase the API gravity, ordecrease the carbon residues in hydrocarbon feedstocks are known.Methods for liquefying solid hydrocarbons and hydrocarbon feedstocks arealso known.

These known methods are, however, directed to specific reactions and donot possess the versatility of generally upgrading a hydrocarbonfeedstock by promotion of a combination of reactions.

It is therefore an object of this invention to provide an economicalmethod for the upgrading of hydrocarbon feedstocks. It is another objectof this invention to provide a method for effecting a multiple upgradingof hydrocarbon feedstocks.

Other aspects, concepts and objects of the invention are apparent fromthe study of this disclosure and the appended claims.

SUMMARY OF THE INVENTION According to the present invention there isprovided a method for upgrading heavy hydrocarbon feedstock whichcomprises reacting the feedstock at an elevated temperature and pressurein the presence of carbon monoxide and in the presence of an activemetal selected from molybdenum, tungsten, nickel, cobalt, copper, iron,and zinc.

In a further embodiment of this invention the reaction of the feedstockat an elevated temperature and pressure takes place in the presence ofcarbon monoxide and an active metal catalyst from the list above andsteam.

The process of the invention will upgrade the applicable feedstocks inone or more ways. The process can substantially desulfurize thefeedstocks. It can decrease the carbon residue and increase the APIgravity of a crude oil. It can reduce the sulfur content of a coal and/or convert a substantial portion of a coal to liquid hydrocarbonproducts.

The above benefits can be obtained Without the need coke formation andwith relatively low formation of cracked low molecular weightbyproducts.

The feedstocks which can be upgraded according to the process of theinvention are heavy hydrocarbon-containing feedstocks. These can becrude oils, heavy hydrocarbon oils, residual hydrocarbon fractions, aswell as solid carbonaceous materials such as coal. These feedstocks cancontain aliphatic and aromatic hydrocarbons as well as acyclic andalicyclic paraffius and olefinic compounds such as those containing upto 40 or more carbon atoms per molecule or those having molecularweights as high as 500 or more. The feedstock can also comprisepulverized coal dispersed in a hydrocarbon oil particularly in ahydrocarbon oil capable of participating in hydrogen exchange reactionsas a hydrogen donor, such as an aromatic oil or a hydrogenated aromaticoil. The heavy hydrocarbon-containing feedstocks will generally benaturally occurring and will generally contain a substantial sulfurcontent, although any crude oil and any coal, including bituminous andanthracite, is applicable.

The catalysts which are applicable for use in the present invention arethose which contain catalytically active metals selected frommolybdenum, tungsten, nickel, cobalt, copper, iron, zinc, and mixturesthereof. These elements can be present in the metallic state or in theform of oxides, or carbonyls, or sulfides, or salts of carboxylic acidssuch as naphthenic acids, or chemically combined with each other, orchemically or physically combined with other metals such as the alkalior alkaline earth metals, particularly barium. Some examples of theseare molybdenum oxide, cobalt molybdate, nickel sulfide, zinc molybdate,copper oxide barium oxide, copper molybdate, magnesium tungstate, ironoxide barium molybdate, tungsten oxide, zinc sulfide, molybdenumhexacarbonyl, cobalt oxide, cobalt naphthenate, nickel naphthenate,barium naphthenate, and the like and mixtures thereof.

Such catalytically active materials can be associated,

the non-acidic type, such as alumina, calcium aluminate, bariumaluminate, magnesium aluminate, bauxite, and the like and mixturesthereof. When such support ma- The conversion temperature will generallybe in the range of from about 550 to about 800 F., preferably from about675 to 720 F. In the lower portion of the temperature range, thereaction can be relatively slow, while in the upper portion of thetemperature range, the

5 terials are present, they can constitute from 40 to about extent ofcoking can become more significant. 95 weight percent of the totalcatalyst composite. The products from the reaction zone generallyinclude In some instances, the catalysts, either supported or unupgradedliquid products, some gaseous products, and supported, can be associatedwith sufiicient, though genminor amounts of coke. The gaseous productscan include erally minor amounts, of alkali or alkaline earth metalsremoved sulfur in the form of carbonyl sulfide and/or to minimize oreliminate acid sites which would otherhydrogen sulfide. wise promotecracking side reactions. The following specific examples show thepreparation Such solid catalysts can be prepared by any suitable of thespecific catalysts of this invention and the method means known in theart. For example, they can be preof using catalysts of this invention indesulfurization, repared by coprecipitation, impregnation, or drymixing. 5 ducing carbon residues and increasing the API gravityWhichever method of preparation is used, the composiusing liquidfeedstock, and liquefying solid hydrocarbon tions should be catalytic inthat they will have a surface feedstock. These examples are meant to beillustrative area of at least about 1 square meter per gram. They areand are not exclusive. generally activated prior to use by calcinationin air at XAM 800-1500 F. Catalyst regeneration is similarly carried EPLE I out Preparation of barium-treated cobalt molybdate catalystPresently preferred catalyst systems are those containing molybdenumassociated with barium. Particularly A banHFn'tIBatedPObaIt molybdiitecatalyst was good results are obtained using a catalyst comprisingcopared by lmPYegnatm? a cmme,rc1auy available cobalt halt molybdatedispersed on a predominantly alumina molybdate catalyst with a solutionof banum acetate. support material and impregnated with Sufiicientbarium Specifically, an alumina-supported cobalt molybdate c atsaltsolution, such as a solution of barium nitrate or alyst (AER? P11334441Aniencan Cyanamlde barium acetate or other carboxylic acid barium salt,to .Company) the ,form of an 1/32 i extrudate was provide from about 1to about 20, preferably from about mlprefgnated m thls manner bysllblectmg f ZOO-gram 2 to about 15, weight percent barium. Anothercatalyst gummy of the Fatalyst to elm/[act with a Solutlon p which hasbeen found to be particularly effective is an mg.55 of ba.num actitate m85 water After lmgreg' unsupported barium molybdate catalyst in whichthe barnatlon j drymg the lmpregnated extrudate P calclnefl ium andmolybdenum are present in approximately at 1100 F. for about 4-5 hours.The composit on of this stoichiometric quantities. catalyst, both beforeand after the incorporation of the The catalysts of the presentinvention are bifunctional banum shown In the followmg Table in thatthey have activity for both the water gas shift re- TABLE 1 actlon andhydrogenatlon- [Composition and properties of cobalt molybdate catalystand its barium The hydrocarbon conversion process of the presentinpmnmted denvmves] ventio n is carried out in liquid phase which inthis ap- 40 Bat-promoted plication means as a totally liquid mixture oras a slurry molggg tg mol l l i of solid hydrocarbons in a liquidhydrocarbon carrier and y 8 1n the presence of carbon monoxide. Theprocess can be ilggg gifgg flgfi 3g 2g carried out both batchwise, suchas in an autoclave, or it Po e di t nn-III: I 71 84 can be carried outcontinuously such as in a fixed bed glifl gg gg gg'gggg i"? 19%;reactor. Any convenient type of reactor can be used. In o yb u WeightP175551?- any event, suflicient carbon monoxide will be present to333,521 ;$5"" 3-3 5% provide a reaction pressure in the range of about1000 t 1 i m to about 5000 psig preferably in the range of about a SSIOHspec rograp ic ana ysis n cated t a presence of trace tn rF,o,M, do.1500 to about 3500 p.s.1.g. Steam, when used, will be a lc ed al sg an npresent in the reaction zone in amounts corresponding to abratio ofliquid waterzliquid hydrocarbon feed of from EXAMPLE 2 a out 1:5 toabout 1:100 by volume. In batch operations, the ratio of solid catalystto feedstock will be in the range i ffifggg giggg cggall ggi g g 01 3i?over of about 0.1 to about 20, preferably from about 1 to y ys about 5,weight percent catalyst based upon the weight A 50/50 blend of Eoceneand Ratawi crude oils were of the feedstock and the reaction time willgenerally be in treated according to the Process of the P 686m inventionthe range of about 0.1 to abount 20 hours. In continuous using thecatalyst described in the preceding example. The fixed-bed processes,the liquid hourly space rate of th conversions were carried out in astirred autoclave for feed Wlll generally be 1n the range of from about0.2 to five hours under several sets of conditions. The essential about10 LHSV. details and the results of these tests are shown in Table 2.

TABLE 2 Run number Feed 0 1 2 3 4 5 '0 h Operating conditions:

Temperature, F......:: 675 7 678 708 660 708 egc pgsggiiljj 00 0 /0 00/300/0 00 3 00 3 1112333530 2.0 11.3 4.0 7.00 1.0 2.0 API' 00 F. gravity20.4 31.9 20.0 20.5 18.9 27.7 Carbon, wt. percent--- 83.7 84.3 86.4585.4 85.4 84.9 84.7 Hydrogen, wt. percent. 11.6 11.2 10.92 11.64 11.910.7 12.09 glfihlrnrgvlfioggrlcennnu 4.0 3.4 2.4 2.9 2.5 3.8 2.8 g e ggnt 1 15.0 40.0 27.5 37.0 0.0 32.4 percent.... 9.07 0.70 0.30 11.04 0.329.70 0.0

TABLE '2Coniti-nue'd Run number Feed 1 2 3 4 5 6 h Gases, mole percent:

Feed=a 50/50 blend 0! Eocene and Ratawl crudes. b 4.8 percent H added.

The data in the table above show that the process of the invention wassuccessful in substantially decreasing the sulfur content of thefeedstock. Further, it is seen that Runs 2-6 using the invention processhave, in several crude oils was subjected to the process of theinvention utilizing both carbon monoxide and steam in 5-hour autoclavereactions. The essential details and the results of these tests areshown in the following Table 3.

TABLE 3 Run number Feed Hzo erude r i Temperature,

Molecular weight Gas Analysis:

Methane. Ethane/ethylene Propane/propylene Heavi 919999.?:oBeorm-waeerecnc instances, increased the API gravity of the oil aswell as reducing its carbon residue value. This was generally ac-,complished with the production of relatively small quantities of coke.The presenceof substantial amounts of car bonyl sulfide in the inventionruns indicate that the substantial portion of the sulfur is removed fromthe crude oil in the form of this compound. In the invention Run 6 inwhich 4.8% water (based upon the feed) was added, there appears to be areduction in the amount of coke which was formed. Run 5 indicates that,under these specific conditions, a temperature higher than 660 F. isdesirable.

EXAMPLE 3 Conversion of crude oil with carbon monoxide-steam overbarium-promoted cobalt molybdate In another series of runs, the same /50blend of ,The results of these tests show that as much as 40% of thesulfur can be removed at temperatures which are.

EXAMPLE 4 Conversion of coal-oil slurry with CO over bariumpromotedcobalt molybdate catalyst A slurry of powdered coal in anthracene oilwas desulfurized according to the process of the present invention in a5-hour autoclave run at 2200-2275 p.s.i.g. The essential conditions ofthe run and. the results are shown in the following Table 4.

TABLE 4 Feed composition AAn- Slurry thracene B of A+ oil l coal 5 B eRun Run 11 Weight percent- 86. 3 l3. 7 100 97. 6 93. 3 Benzene insolublematter, weight percent. Nil 99+ 13. 7 8 63 10. 75 Pyridine insolublematter, weight percent Nil 99+ 13.7 3. 2 5. 0 Catalyst, weightpercent... 0 5 Temperature, F 670 750 Conversion of coal To benzenesolnbles, percent 37. 2 21. 5 To pyridine solubles, percent 46. 7 63. 5Composition and properties:

Carbon, weight percent 90. 6 68. 0 87. 6 89.6 91. 26 Hydrogen, wt.percent..- 6. 1 5. 0 5. 88 5. 9 6. 26 Oxygen, wt. percent-..-- 1. 2 u11. 28 2. 58 2. 2 1. 7 Nitrogen, wt. percent.. 0.78 1. 0 0.81 0. 73 0.98Sulfur, wt. percent 0. 69 2. 97 0. 90 0. 61 0. 54 Ash, wt. percent Nil11. 75 1. 61 1. 56 Carbon residue, percent.. 2. 78 65. 11. 50 10. 89 6.62 Molecular weight 1 69 Sulfur removal, percent 0 32. 89 40. 0

Anthracene oil contained primarily pheneanthrene. b Washed southernIllinois coal.

v Physical mixture, assuming no reaction:

' Moisture-free basis.

6 By diflerence.

Analyses of the gaseous products from these runs are 30 shown in thefollowing table. The original gas was comprised solely of CO which wasused to pressurize the autoclave to 100 p.s.i.g. at about 75 F. at thestart of the test.

These data clearly indicate that COS is the primary reaction product.Carbon dioxide can be derived from the reaction of CO withoxygen-containing derivatives of the coal products. H 5 can be formed byhydrogen exchange with the aromatic compounds such as phenanthrene whichis a major component in the anthracene oil.

EXAMPLE 5 Liquefaction of coal with CO-steam over bariumpromoted cobaltmolybdate catalyst In this example, a slurry of coal (a washed coalobtained from southern Illinois) in anthracene oil was subjected to theprocess of the present invention in a 5-hour autoclave run. The reactionconditions included the presence of carbon monoxide, steam, andcatalyst. The catalyst was the same as that prepared in Example 1. The

essential conditions and results of these runs are shown in Table 5below.

TABLE 5 Run number Feed 12 13 Operatin conditions:

Coal anthracene oil retio....-.-.-: 1/6. 4 1/6. 3

Water/total hydrocarbon feed 0. 163 0. 17

Catalyst, BaO on lit-4311, wt. percent. 0.0 5. 2

Temperature, F 708 700 Pressure. p s l w 3, 250 3,375 Liquid product:

Total recovery, wt. percent 100.00 95. 0

Benzene insolubles, wt. percent.. 16. 3 5. 4.5 3. 59

Pyridine insolnbies, wt. percent 16. 3 2. 44 1. 75 Conversion of coal:

To benzene sols., percent....- 74. 0

Carbon residue, (Rams) percent-. 10.1

To pyridine sols., percent 87. 4

BIG mol ratio 0. 87

Sulfur, wt. percent 0. 44

I Moisture-free basis.

glCalculated properties oi physical=83.3% anthracene oil and 16.7% coThe data in the above table show that the catalytic invention Run 13converted 74.0% of the coal into benzene soluble matter, in addition tosubstantially reducing the sulfur content of the coal slurry.

EXAMPLE 6 Liquefaction of coal with (DO-steam using soluble catalysts Ina manner closely analogous to that of the preceding example, a similarcoal/anthracene oil slurry was converted in a 5-hour autoclave runemploying carbon monoxide, steam, and several combinations ofoil-soluble metal naphthenates. The essential conditions and results ofthese runs are shown in Table 6.

' TABLE 6 Run number Feed I 14 15 16 17 Test conditions:

Coal/anthracene oil ratio 1/4.5 1/4 5 1/4 5 1/4. 5

Water/hydrocarbon ratio... 1/5.5 1/5 5 1/5 5 1/5 5 Catalyst (asnaphthenates) Ba/Ni Ba/Co Ba/Mo Ba/Fe Catalyst added, wt. percent 4.4/36 5.5/3 6 5. 5/3 6 5.5/3 6 Temperature, F 705 71 610 Pressure, p.s.i.g3, 200 3, 400 3, 400 3, 400 Liquid product:

Total recovery, wt. percent 9S. 6 B 101. 5 98. 5 95. 6

Benzene insolubles, wt. percent. 16. 3 5. 63 5. 49 4.80 5. 67

Pyridine insolubles, wt. percent 16. 3 3.79 2.99 5.4 3.79

a-Hexane insolubles, wt. percenL.-- 16.3 10. 7 12. 5 Conversion of coalrcent:

To benzene soiub es 68. 7 67. 1 65. 3 66.

To pyridine solubles- 77. 1 82. 0 67. 7 77. 4

To hexane solubles 35. 25. 0 13. 6

Carbon residue, percent 13.02 9. 08 8. 49 8.82

ulfur, wt. percent 1.00 0 63 0. 43 0. 53 0.43

I Properties of blend as calculated from composition of ieed used intests.

As corresponding metal naphthenates. Contains some coke derived from theCO. d Moisture-free basis.

The data above show that the combination of barium naphthenate saltstogether with nickel, cobalt, molybdenum, or iron naphthenate salts alsocatalyze the liquefaction of coal in the presence of carbon monoxide.

EXAMPLE 7 Conversion of crude oil with CO-steam over barium molybdatecatalyst In this series of runs, a 50/50 mixture of Eocene and Ratawicrude oils were desulfurized according to the process of the presentinvention using an unsupported barium molybdate (46.2 weight percent Ba)catalyst. The tests were conducted in a 300 C. rocking autoclaveequipped with a quartz liner. The crude oil, catalyst, and water, ifused, were added to the autoclave which was then closed and flushedseveral times with nitrogen. After pressuring to 1000 p.s.i.g. with COat room temperature, heat was applied as rapidly as possible until thedesired operating temperature was reached. The tests were of five hoursduration. The pressures shown in the table were at the beginning of thereaction period. As water was consumed, pressures were distinctly lowertowards the end of the tests.

TABLE 7 25 The data show that, without a catalyst, no substantialReasonable variation and modification are possible within the scope ofthe foregoing disclosure and the appended claims to the invention theessence of which is that a heavy hydrocarbon feedstock can be reacted inthe presence of carbon monoxide and a catalyst comprising an activemetal and an alkaline earth metal at elevated temperatures and pressuresto improve the quality of the reactive material.

I claim:

1. A method for desulfurization of heavy liquid hydrocarbon feed stockcomprising:

Run number Feed 18 19 20 21 Operating details:

Temperature, F I 708 711 709 728 Pressure, p.s.i.g 2, 200 2, 200 2, 6504, 100 BaMoO4, wt. percen None 4. 4. 55 4. 0 Metal naphthenate None NoneNone None Weight, percent naphthenate None None None None Water, wt.percent None None 4. 55 16. 0 Coke, wt. percent 7. 2 1. 67 2. 3 2. 33Liquid product:

Weight, percent 96. 0 96.2 96. 3 API gravity, 60 F- 20.4 26. 0 24. 4 24.8 23. 7 Carbon, wt. percent..- 83. 7 84. 8 83. 7 84. 3 86. 2 Hydrogen,wt. percent 11. 6 11. 7 11. 7 11.9 10. 7 Sulfur, wt. percent 4. 00 b 3.6 3. 1 3. 2 2. 8 Sulfur removed, percente 10. 0 24. 4 22. 0 32. 7 Carbonresidue, percent- 9. 07 6. 14 8. 17 7. 72 6. 57 Gaseous materials, molpercent:

728 728 a, 900 3, 850 2. 7 2. 7 Co Ni 1. 37 1. 37 13. 7 13. 7 1. 55 3. 0

I IO-hour run. b Converted to yield basis. Based on 3.6 value.

11 (a) passing into a reaction chamber a reactant consisting essentiallyof carbon monoxide, said reactant present in amounts suflicient toprovide a reaction pressure in a range of about 1500 to about 3500p.s.i.g., and

(b) reacting said hydrocarbon feed stock in the liquid phase with saidcarbon monoxide reactant in the presence of a catalytically active metalselected from molybdenum, tungsten, nickel, cobalt, copper, iron, andzinc, for a time and at a temperature sufiicient to carry out theprocess of desulfurization 2. The method of claim 1 wherein saidcatalytically active metal is associated with analkali metal or analkaline earth metal.

3. The method of claim 1 wherein said catalytically active metal isassociated with a catalytic support selected from the group consistingof alumina, bauxite, Group IIA metal aluminate and mixtures thereof,said support comprising from about 40 to about 95 weight percent of thetotal catalyst composition.

4. The method of claim 1 wherein said temperature is in the range fromabout 550 to about 800 F.

5. The method of claim 4 wherein said reaction is carried out batchwiseand the ratio of solid catalyst to feedstock is in the range of about0.1 to about 20 weight percent catalyst based on weight of feedstock andthe reaction time is in the range of about 0.1 to about 20 hours.

6. The method of claim 5 wherein steam is present in the reaction zonein a ratioof liquid water to liquid hydrocarbon feed of from about 1:5to about 1:100 by volume.

7. The method of claim 4 wherein said reaction is continuous in a fixedspan and the liquid hourly space velocity of the feed is in the range ofabout 0.2 to about 10.

8. The method of claim 7 wherein steam is present in the reaction zonein a ratio of liquid water to liquid hydrocarbon feed of from about 1:5to about 1:100 by volume.

9. The method of claim 3 wherein the catalyst is barium-promoted cobaltmolybdate.

References Cited UNITED STATES PATENTS 2,242,387 5/1941 Boyd 208-208 R2,917,532 12/1959 Watkins 208--209 FOREIGN PATENTS 413,181 2/1966 Japan208-209 DELBERT E. GANTZ, Primary Examiner G. J. CRASANAKIS, AssistantExaminer US. Cl. X.R.

